'{'UK  SOLUBILITY  OF  PHENOL  IN  AQUEOUS 
SOIAITIONS  OF  GLUCOSE,  GLYCEROL, 
ACETONE,  ANJ)  UREA 


liY 


IRNTNG  n.  MORGAN 


THESIS 

FOR  Till-: 

J)EGREE  OF  BACHELOR  OF  SCIENCE 

IN 

CHEMICAL  ENGINEERING 


COLLEGE  OE  LIBERAL  ARTS  AND  SGIP^NCES 
UNIVERSITY  OF  ILLINOIS 


1922 


I 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/detaiis/soiubiiityofphenOOmorg 


UNIVERSITY  OF  ILLINOIS 


March. .1,5 

THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

.1  rv  i.n.g.. . B anc.r.o  ft. , , ,Mo  r gan 

ENTITLED Th.e...So.l.uMIlty...M..Ph.eh.Ql..l,h..Aaue.Qus....So.l.u.tiQTi§. 

of  Glucose,  Glycerol,  Acetone  and  Urea. 

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF Pach.elgr....o.f  ....S.o.i.e.n.c.e,...in...C.h.e.  


Approved  ; 


Instructor  in  Charge 


HEAD  OF  DEPARTMENT  OF 


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ACKNOIinjEDGLIENT 


I wish  to  express  my  appreciation 
to  Dr.  J.  H.  Reedy,  for  his  cooperation 
and  to  thank  him  most  sincerely  for  the 
many  valuable  suggestions  offered  during 
the  preparation  of  this  thesis. 


Tabls  of  Contents 

1 

j 

I. 

INTRODUCTION 

Page  ! 

1 

II. 

HISTORICAL 

2 

III. 

EXPERIMENTAL 

1.  Materials 

4 

S.  Procedure 

4 

IV. 

RESULTS 

1.  Glucose  Solutions 

8 

2.  Glycerol  Solutions 

9 

3,  Acetone  Solutions 

10 

4.  Urea  Solutions 

10 

V. 

DISCUSSION 

1.  Solvent  Action  of  Organic  Compounds 
on  Phenol 

17 

3.  Formation  of  Addition  Product  in 
Acetone  Solutions 

30 

3.  Group  Influences 

31 

VI. 

SUMiaRY 

33 

VII. 

BIBLIOGRAPHY 

24 

Table  of  Plates 


Page 

I.  Arrangement  of  apparatus  in  Thermostat  7 

II.  Specific  gravity  Curve  for  Glucose  Solutions  10 

III,  Solubility  of  Phenol  in  Glucose  Solutions  11 

IV,  Specific  Gravity  Curve  for  Glycerol  Solutions  13 

V,  Solubility  of  Phenol  in  Glycerol  Solutions  14 

VI.  Specific  Gravity  Curve  for  Acetone  Solutions  15 

VII.  Solubility  of  Phenol  in  Acetone  Solutions  16 

VIII,  Specific  Gravity  Curve  for  Urea  Solutions  18 

IX.  Solubility  of  Phenol  in  Solutions  of  Urea  19 


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PART  I 
INTRODUCTION. 

Very  little  has  been  done  in  determining  whether 
mixed  solutions  of  high  concentration  follow  a definite 
solubility  law.  Some  solutes  repress  the  solvent  power 
of  water  but  being  solvents  in  themselves,  the  total 
solubility  of  the  solution  is  increased.  Other  solutes., 
simply  diminish  the  solubility  of  their  own,  the  total 
solubility  of  the  solution  is  decreased.  The  purpose 
of  this  problem  is  twofold.  First  to  ascertain  the 
solubility  behavior  of  phenol  in  aqueous  solutions  of 
glucose,  glycerol,  acetone,  and  urea,  and  second,  to 
determine  if  there  is  a similar  relation  between  this 
and  the  solubility  of  benzoic  and  salicylic  acids  in 
like  solutions. 


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- 3 - 

PART  II 

HISTORICAL, 

(1)  (3) 

Nernst  and  A.  A.  No^es  both  agreed  that  the  concen- 
tration of  molecules  of  a solute  remains  unchanged  by  the 

(5) 

presence  of  other  substances,  Arrhenius  took  exception  to 

this  and  by  using  Noyes'  ovm  data  on  the  solubility  of  thallium 

chloride,  showed  that  the  solvent  power  of  a given  medium  was 

diminished  by  the  presence  of  dissolved  substances.  This  is 

shown  conclusiiKely  in  the  well  known  commercial  process  of 

salting  out,  A more  or  less  accepted  theory  expounded  by  Jones 

and  his  collaborators  suggested  that  the  molecules  and  ions  of 

a solute  in  a water  solution  of  the  solute  formed  hydrates  and 

thus  used  up  some  of  the  water  solvent,  which  caused  a relative 

decrease  in  the  solubility  of  the  water  content  of  the  solution. 

(5) 

Smits  and  Maarse  found  that  a hydrate  of  phenol  existed  and 


(4) 


(6) 


that  it  had  a considerable  range  of  metastable  equilibrium. 

This  not  only  bears  out  the  theory  of  hydrate  formation,  but 
carries  considerable  weight  in  the  present  problem,  Washburn 
dismisses  the  subject  briefly  by  stating  that  in  working  with 
concentrated  solutions  where  the "thermo dynamic  environment"  is 
not  constant,  each  solution  must  be  treated  as  a problem  by  it- 
self and  the  quantitative  relations  connecting  its  properties 
with  composition  must  be  derived  by  direct  experiment.  Lovell 
in  working  on  the  solubilities  of  benzoic  and  salicylic  acids  in 
aqueous  solutions  of  glucose,  glycerol,  acetone,  and  urea,  found 
that  the  organic  solutes  exerted  a solvent  action  on  the  acids. 


(7) 


T 'V 


- 3 - 

Also  that  the  total  solubility  in  all  cases  was  found  to  be 
lees  than  the  combined  solubilities  of  the  components  of  the 
solutions  acting  separately.  He  developed  an  expression  for 
the  solubility  in  a binary  medium  as  follows:  Let  A and  B 

be  two  solvents  where  a and  b represent  the  number  of  moles  of 
each  present  and  S the  solubility.  The  expression  then  be- 
comes S - aSA  - bSg  abk. 


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^ 4 - 

PART  III 
EXPERIMENTAL 

Materials  - In  carrying  out  an  experiment  of  this  nature 
it  is  necessary  to  have  a substance  of  comparatively  low 
solubility  and  negligible  ionization  in  aqueous  solutions. 

Also  there  must  be  a reasonably  accurate  method  of  determining 
the  substance  quantitatively  from  water  solutions.  Phenol 
satisfied  all  three  of  these  conditions  although  the  quanti- 
tative determination  of  it  proved  to  be  somewhat  difficult. 

The  phenol  used  was  the  crystallized  product  sold  by  the 
J.  T.  Baker  Chemical  Company,  and  had  a melting  point  of  40.5® 
and  a solubility  of  thirteen  grams  in  one  hundred  grams  of 
water.  The  glucose,  glycerol,  acetone,  and  urea  were  all  of 
the  highest  grade  available.  Solutions  of  the  latter  were 
prepared  of  concentrations  varying  from  1^  to  35^  by  weight. 
These  solutions  were  only  prepared  as  needed, as  it  was  found 
that  the  stock  solutions  of  glucose  and  glycerol  could  not  be 
kept  any  length  of  time  without  a noticeable  change  due  to 
enzyme  action.  The  specific  gravity  curves  were  drawn  from 
data  taken  from  Landolt  and  Bornstein  Tabellen, 

Procedure  - 200  cc,  of  the  mixed  solvent  solution,  i.e. 
ifo  glucose  in  water,  was  placed  in  a 500  cc.  Erlenmeyer  flask 
with  an  excess  of  solid  phenol.  The  flask  was  equipped  with 
a centrifugal  stirrer  and  placed  in  a thermostat  carefully 
regulated  at  25® C.  Eight  of  these  separate  solutions,  four 


- 5 - 

solutions  in  duplicate,  were  placed  in  the  thermostat  at  one 
time  as  shown  in  Plate  I,  and  stirred  simultaneously  for  about 
twenty  hours.  The  excess  phenol  was  then  allowed  to  separate 
out  by  standing  and  two  10  cc.  portions  of  the  aqueous  layer 
removed  for  analysis.  Tlie  quantitative  procedure  for  deter- 
mining the  amount  of  phenol  dissolved  by  the  mixed  solvent 
solution  caused  some  difficulty  at  first.  The  method  of  adding 
an  excess  of  liquid  bromine  to  the  solution  was  attempted,  thus 
forming  the  insoluble  tribromphenol.  The  excess  bromine  was 
determined  by  adding  potassium  iodide  and  titrating  the  iodine 
thus  liberated  with  tenth  normal  sodium  thiosulphate  solution. 

The  chief  difficulty  encountered  with  this  method  was  the 
volatility  of  the  liquid  bromine.  Koppenshar' s modification  of 
this  method  was  then  tried  in  thich  the  original  10  cc.  sample 
taken  was  diluted  a thousand  times  and  an  excess  of  a bromide  - 
bromate  solution  (3,784  grams  KBrOa' and  10  grams  KBr  to  1 liter) 
added  together  with  5 cc.  HCl.  The  solution  was  allowed  to 
stand  until  the  tribromphenol  had  formed  and  settled.  The 
excess  bromine  present  was  then  determined  by  adding  KI  and 
titrating  with  tenth  normal  thiosulphate  solution.  The  main 
difficulty  in  this  method  was  the  large  experimental  error  caused 
by  the  high  dilution,  but  this  error  was  much  smalled  than  that 
found  in  the  first  method.  Because  of  the  possible  error, 
duplicate  runs  were  made  on  each  of  the  solvent  solutions  and 
check  determinations  were  made  of  the  phenol  dissolved  in  each 
of  the  duplicate  samples.  The  average  of  the  four  determinations 


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- 8 - 

PART  IV 
RESULTS 

Glucose  - The  results  of  the  solubility  of  phenol  in  glucose 
water  solutions  are  tabulated  in  Table  I and  the  graphical  rep- 
resentation is  given  in  Plate  III,  The  black  line  shows  the 
solubility  of  phenol  in  glucose-water  solutions  in  grams  per 
100  grams  of  solution,  ?;hile  the  red  line  shows  the  calculated 
solubility  of  phenol  in  the  water  present  in  100  grams  of  the 
glucose-water  solutions.  Because  of  the  dilution  to  which  the 
phenol  solution  is  subjected  during  the  process  of  determining 
the  amount  of  phenol  which  went  into  solution, a slight  exper- 
imental error  will  produce  a very  appreciable  discrepancy  in 
the  final  result.  For  example,  0.1  cc.  difference  in  the  amount 
of  the  thiosulphate  solution  used  in  titrating  the  excess  of 
bromine  added  will  produce  a difference  of  0.4  grams  in  the 
weight  of  phenol  found  to  be  present.  The  results  have  there- 
fore been  interpreted  to  mean  that  the  black  and  red  lines  should 
practically  coincide  on  the  graph.  In  other  words  the  presence 
of  glucose  lowers  the  solubility  of  the  solution  but  does  not 
alter  the  solvent  power  of  the  water  present.  An  alternate 
explanation  would  be  that  the  solubility  of  the  phenol  in  the 
glucose  hydrate  is  the  same  as  that  of  water. 


-■  ..*■-•■>-■ 


( 


- 9 - 


TABLE  I 


The 

Solubility 

of  Phenol  in  Glucose 

Solutions. 

Glucose 

Sp.  Gr. 

Grams  phenol /l 00  gras. 

sol. 

Gms.  Phenol 
dissolved  in 
water  present 

0 

1.0000 

13.001 

in  100  gms.  of 
solution. 
13.001 

1 

1.0037 

13.633 

13.871 

5 

1.0171 

12.133 

13.351 

10 

1.0379 

11.770 

11.700 

15 

1.0585 

11.393 

11.051 

30 

1.0793 

10. 488 

10.401 

35 

1.1000 

9.448 

9.751 

Glycerol  - Table  II  and  Plate  V show  the  solubility  of 
phenol  in  glycerol -water  solutions.  In  this  case  as  before, 
the  red  line  represents  the  solubility  of  phenol  in  the  water 
present  in  100  grams  of  solution  and  is  the  same  in  the  case 
of  glucose  since  it  is  a function  of  the  percent  water  present 
in  the  solution.  However,  the  black  curve  representing  the 
solubility  in  grams  per  100  grams  of  solution  shows  a marked 
deviation  from  the  similar  curve  for  glucose.  The  solubility 
increases  with  an  increase  in  the  percentage  glycerol  present. 
This  increase  in  the  solubility  is  comparatively  small  in  low 
concentrations,  but  increases  very  rapidly  above  15'^.  This  shows 
that  glycerol  solutions  are  better  solvents  for  phenol  than  those 
of  glucose,  and  leads  to  the  belief  that  glycerol  itself  has  a 
specific  solubility  for  phenol.  This  increase  in  solubility, 
due  to  the  presence  of  glycerol  cannot  be  assumed  to  be  additive 
as  the  solubility  curve  is  not  a straight  line. 


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I 


- 13 


Glycerol  Sp.  Gr. 


from  curve 

0 

1.0000 

1 

1.0006 

5 

1.0080 

10 

1.0306 

15 

1.0360 

30 

1,0514 

35 

1.0617 

TABLE  II 


Gms.  phenol  per 
100  gais.  solution 

13.001 

13,387 

14.065 

14.890 

17.566 

37.603 

51.336 


Gms.  phenol  dissolved 
in  water  present  in 
100  gms,  solution, 

13,001 
13.871 
13.351 
11.701 
11.051 
10,  401 
9.751 


Acetone  - The  results  of  the  determinations  with  acetone- 
water  solutions  are  given  in  table  III  and  Plate  VII,  The 

solubility  of  phenol  showed  a very  marked  decrease  in  solubility 

in  solutions  up  to  5'^  acetone,  but  at  higher  concentrations  the 

solubility  became  constant.  The  decrease  in  solubility  was  much 

greater  than  that  in  the  glucose-water  solutions. 


TABLE  III 

Gms.  phenol  dissolved 


Glycerol 

Sp.  gr. 
from  curve 

Gms.  phenol  per 
100  gms.  solution 

in  water  present  : 
100  gms.  solution 

0 

1.0000 

13.001 

13.001 

1 

.998 

11.691 

13,871 

5 

.993 

8.333 

13.351 

10 

.985 

8.083 

11.700 

15 

.976 

8.137 

11.051 

30 

.969 

8.175 

10.401 

35 

.962 

8.375 

9.751 

Urea  - The  results  obtained  from  the  urea-water  solutions 
are  tabulated  in  Table  IV  and  ploted  on  Plate  IX.  The  urea 
increased  the  solubility  of  the  phenol  in  the  urea-water  solu- 
tions in  a manner  similar  to  that  of  glycerol.  In  this  case 
however,  the  marked  increased  did  not  occur  until  a 30^  conceu 


SpE.c/Fic  Cma^JiTY  Curve,  For  Vrhyinq  Percents 
Of  Ctlycerol  In  Wrter. 


9 


■? 

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Granin  Phenol DiS'&olved 

__i£0 ^0  - 


Specific  Gravity  Curve  For  VnnYiNQTEHCENTQ  Of 

Rcetone  In  Wrtep. 


<J) 


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S0LU3JLITY  Of  Phenol  /n  V^nviNa  Pelrcent 
Solutionis  Of  PIcetone. 


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- 17 


tratration  was  reached,  while  with  glycerol  the  greater  increase 
occurred  above  15'^  concentration. 


TABLE  IV. 

Gms. phenol  dissolved 

urea  Sp.  Gr. 

Gms. phenol  dissolved 

in  water  present  in 

from  curve 

in  100  gms.  solution 

100  gms.  of  solution 

0 

1.0000 

13.001 

13.001 

1 

1.0035 

13.308 

13.871 

5 

1.0135 

14.  874 

13.351 

10 

1.0365 

16.357 

11.700 

15 

1.0380 

19.  403 

11.051 

30 

1,0535 

31.047 

ID. 401 

35 

1.0660 

39.569 

9.751 

PART  V 

DISCUSSION.' 

Solvent  Action 

of  Organic  Compounds  ^ 

on  Phenol  - From  the 

results  of  these  determinations  it  is  apparent  that  the  solU' 


bility  of  phenol  in  mixed  aqueous  solutions  is  decreased  by 
the  presence  of  glucose  and  acetone  and  increased  by  the  presence 
of  glycerol  and  urea.  In  the  case  of  glucose,  the  decrease  in 
the  solubility  of  the  phenol  was  practically  inversely  propor- 
tional to  the  concentration  of  the  solution,  showing  that  the 
glucose  neither  repressed  or  aided  the  solvent  action  of  the 
ViTater.  This  does  not  exactly  follow  the  theories  of  Noyes 
and  Arrhenius,  that  the  presence  of  dissolved  molecules  reduces 
the  solvent  power  of  water.  However,  it  may  be  possible  that 
the  glucose  alone  has  a slight  solvent  power  for  phenol  which 
would  overcome  any  decrease  in  the  solvent  power  of  water  that 
the  presence  of  glucose  might  incur.  Lovell  found  similar 


30 


Specific  Crt^avity  ^94 


^or 


Crram^  T^henol  D/oso/ved 


- 20  “ 

conditions  existing  in  the  solubility  of  benzoic  and  salicylic 
acids  in  glucose  solutions.  The  solubility  of  the  two  acids 
was  decreasec,  but  there  was  a slightly  higher  solubility  in 
the  solution  than  in  the  water  present  in  an  equivalent  amount 
of  solution.  The  glycerol  and  urea  produced  an  increase  in  the 
solubility  of  the  phenol.  This  shov/s  that  glycerine  and  urea 
exert  a solvent  influence  on  the  phenol.  These  again  are  like 
the  results  found  by  Lovell  as  to  the  solubility  of  benzoic  and 
salicylic  acids  in  solutions  of  glycerol  and  urea. 

Formation  of  Addition  Product  in  Acetone  Solutions  - The 
acetone  solutions  gave  remarkably  peculiar  results.  The  solu- 
bility of  the  phenol  in  the  acetone-water  solution  fell  far 
below  the  solubility  of  the  phenol  in  the  water  present  in  the 
same  solution.  The  solubility  finally  became  constant  above 
5'^  solutions.  With  similar  solutions  Lovell  found  that  the 
solubility  of  benzoic  and  salicylic  acids  increased  with  an 
increase  in  the  concentration  of  acetone.  In  the  case  of  phenol, 
therefore,  presuming  there  should  be  a similarity  for  all  solu- 
tions, an  addition  product  must  have  been  formed  between  the 
phenol  and  acetone,  or  there  was  a marked  hydration  between 
the  phenol  and  water.  The  latter  does  not  seem  reasonable, 

since  there  is  no  difficulty  of  a like  nature  experienced  with 

(8) 

any  of  the  other  organic  solutes  used.  Schmidlin  and  Lang 
found  a compound  of  acetone  and  phenol  which  was  in  the  form 
of  long  needles  melting  at  15°C.  There  being  no  better  name 

available,  they  called  it  Phenol-acetone.  This  assists  in 


s • 


u 


4 


'I 

I 


w 

t 


‘•:W 


'C. 


,L 


' 4 

T 


\ . 


. ‘ I 


j. 


f 


1 i 


f.J  "Ti  . i- 


i>; 


u 


t . i 


< * Cj  * 'i>t  \ 


■;*'j  ,r/:r  ij 


•<  v* . *. 


1' 

'r 


. h 
I 


<1 

•’I 


5 


J 


r • 


t 


i 


- 31  - 

bearing  out  the  assumption  of  an  addition  product  being  formed. 
Another  reason  for  assuming  the  formation  of  the  so  called 
phenol  acetone  can  be  found  by  means  of  the  Phase  rule.  The 
solution  has  one  degree  of  freedom  (F),  that  of  temperature, 
and  consists  of  three  components  (C)  namely,  water,  acetone, 
and  phenol.  By  substituting  in  the  general  phase  rule  formula 
F = C - 3 - P and  solving  for  the  number  of  phases  present, 

(P)  it  is  found  that  there  should  be  four  phases  present. 

Only  three  of  these  phases  can  be  accounted  for,  the  vapor 
phase,  the  solution  phase,  and  the  phenol  phase.  It  can  be 
assumed  therefore,  that  the  fourth  phase  must  be  some  combin- 
ation of  the  phenol  and  acetone.  Also  according  to  the  above 
phase  rule  conditions  the  concentration  of  the  phenol  in  solu- 
tion should  remain,  which  it  does;  as  can  be  seen  from  the 
fact  that  the  curve  is  perfectly  vertical  above  5^  acetone. 

Group  Influences  - In  making  a comparison  of  group  in- 
fluences or  the  effects  of  certain  groups  on  organic  solvents, 
it  was  found  that  OH  groups  apparently  reduced  the  solubility. 
Phenol,  benzoic  acid,  and  salicylic  acid  all  showed  lower  solu- 
bility in  glucose  solutions  than  in  glycerol  and  the  former  has 
many  more  OH  groups  than  glycerol.  The  CH3  group  in  the  acetone 
aided  the  solubility  of  the  benzoic  and  salicylic  acids,  but  due 
to  the  formation  of  the  addition  product  between  phenol  and 
acetone,  the  actual  solubility  of  phenol  in  acetone  solutions 
was  not  obtained  and  consequently  a comparison  with  phenol 


cannot  be  made  in  this  case.  The  CO  group  exerted  no  apparent 
influence  on  the  solubility  of  any  of  the  compounds  used  and 
therefore  it  is  concluded  that  this  group  does  not  have  any 
active  influence  on  the  solubility.  However,  the  NHg  groups 
have  quite  a noticeable  effect  on  the  solubility.  The  phenol, 
benzoic  acid,  and  salicylic  acid  were  all  more  soluble  in  urea- 
water  solutions  than  in  any  other  of  the  mixed  solutions. 


t'l  . ...  ^,.  . w ._  :•' ,i‘..r-  •i^vw-f?' ■’. 


W *V  < . 

L J ^ •■:/<J^^i  C:^  ♦iiSA.®  Aii4F^;.J^jbil 

■ '.  - i , . ^ , . V ' : 


» , • n 


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Vt 


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c/‘ 

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»'•'  V.  ' ,',  ,»l 


V ' f 


- 33  - 

PART  T 
SUJmRY 

1.  The  solubility  of  phenol  has  been  determined  at 
35®  in  solutions  of  glucose,  glycerol,  acetone, 
and  urea  varying  from  1-35^  by  weight. 

3.  These  solutes  with  the  exception  of  glucose  and 
acetone  have  a solvent  action  on  phenol, 

3.  The  formation  of  an  addition  product  with  phenol 
in  acetone  solution  was  shown. 

4.  A comparison  was  made  of  the  solubility  of 
phenol  with  benzoic  and  salicylic  acids  in  the 
same  kind  of  solutions. 

5.  A comparison  was  made  of  the  group  influences 
on  the  solubility  of  phenol,  benzoic  acid, 
and  salicylic  acid. 


- 24  - 


PART  VIII 
BIBLIOGRAPHY 

1.  Nernst  - Theoretical  Chemistry,  p.  357  (1911) 

2.  A.  A.  Noyes  - Z,  Physik,  Chem,  243  (1890) 

3.  Arrhenius  - Z.  Physik.  Chem. , 224  (1899) 

4.  H.  C.  Jones  - Z.  Physik.  Chem.  , 1^,  419  (1894) 

5.  Schmitts  and  Jiaa.rse  - Proc.  Acd.  Wettenschappen, 

14,  192  (1907) 

6.  Washburn  - Prin.  of  Phys.  Chem. , p.  179  (1915) 

7.  C.  B.  Lovell  - Bachelor  Thesis  U.  of  I.  (1921) 

8.  Schmidlin  and  Lang  , Ber.  43,  2860-20. 


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